Et manufactures de produits chimiques du nord



Reissuecl. Nov. 2 5, 1930 UNITED STATES,

Annals HENRI vIo'roR' DURR, or PARIS, FRANCIQASSIGNOR T COMPAGNIE'NATIONALE PATENT OFFICE DE MATIEBES COL ORAN TES ET MAN UFACTURES DE PRODUITS CHIMIQUES DU NORD REUNIES, ETABLISSEMENTS KUHLMANN, OF IARIS, FRANCE, A CORPORATION OF FRANCE m Drawing. Original No. 1,739,447, dated December'lo, 1929, Serial No. 329,940, filedl'anuary 2, 1929,

BESTNOUS CONDENSATION" PRODUCT and in France December 31, 1927. Application for reissue filed August 19, 1930. Serial No. 476,446.

In'the specification of my United States Patent No. 1,739,446, I havedescribed the preparation of new esters andderivatives and their resinous condensation products by esterifying thealcohol radicals of a polyhydric alcohol, glycerine for example, by means of a mixture of an aromatic polybasic acid, phthalic anhydride for example, and one ormore natural resins, such as colophony, m'anila gum, etc., in such a manner that only apart of the hydroxyl content of the alcohol is replaced by the acid, another part is replaced by the natural resin (through its resinic acid), and some free hydroxyl nature. If the resinic acid of a natural resin groups remain, the number of hydroxyl groups replaced. by the acid and natural resin and those remaining free being varied at will according to the ester required.

It will be understood that for the purpose of the present invention, the terms polybasic acids and natural resins are of a. general character, and nclude polybasic anhydrides in the one case, and natural gums in the other.

' Glyceryl phthala-te resins can be considered as polymers'of glyceryl phthalate, all the free hydroxyl groups of the glycerine being replaced by the phthalic anhydride usually used in excess, so that these resins may be represented by the general formula- 0 0 NJ) at Good 0d 0d ed where 7 indicates the degree of polymerization. The products obtained by heating with resin are derivatives of this fundamental base. p is a general description of the The above theory in regard to the resinous products as originated in the laboratories of the General Electric Co.

In the present invention, the construction of the resin base is of a somewhat dilferent be represented by R-COOH, then the general form of the new resinous products may be represented somewhat as follows, at having the same meaning as before:

oils-organ, on

matron-on From this, it will be seen that the base isof a form which is distinctly novel, no reference to any such base being made in the prior art. 1

The object of the present invention is to --produ ce condensation products of these new resinous products with linseed oil or other siccative oil witha view to obtaining compounds possessing properties similar to those of the oil varnishes.

New industrial products have tained by heating these new resins with a siccative oil, linseed oil for example, in an auto clave, without the agency of a solvent.

A homogeneous mass in the form of a more or less viscous liquid mass is obtained under these conditions. By dissolving the mass in been obdifferent solvents singly or mixed together,

arising from the distillation of coals, tars and petroleums (such as benzol, toluol, xylol, petroleum, naphtha, coal-tar oil, etc.) varnishes are obtained, drying above 110120 and used in the. electric industries and ovenor furnace varnishing. K

The films obtainedv with these varnishes have remarkable qualities of adherence and flexibility as well as a high dielectric strength. For example, a varnish baking at 300 and giving a film having a dielectric value of 1520 volts to one hundredth of a millimetre (average of 8'tests) has been obnary temperature, of a our, slightly fluorescent.

EacampZe I I 450 parts of linseed oil are placed ina well stirred autoclave together with 450 parts of resin prepared. as described in-ExampleI of my said atent No. 1,7 39,446, to wit,'by a'dding a mixture of phthalic anhydride and colophony (acid value=162 .5) to glycerine, the proportions being 285, 200 and 240 parts respectively, at 110, raising the temperature to 260 in 1520 hours, and after main-,

taining the reaction mixture at this tempera ture for- 2hours, running the product off.

. The mass of oiland resin is heated for 16 hours at 210.

kilos. p

The mass is then left to cool at 50-60 and tests made to ascertain if it be completely homogeneous. If it does not happen to be so, it is'heated again for 8 hours at 250 and longer if necessary.

The mass is in a viscous form at the ordigreenish yellow col- The pressure rises to 5 or 6 This example is not restrictive with-regard to the proportions of siccative oil and resins, the nature of the resin and of the siccative oil, theduration and temperature ofthe heating which are naturally variable .,with I the I. we

resin or mixture of resin used and the prod,-

uct desired.

' Emam-ple II 100 parts of the condensation mass prepared under the conditions of Example I are diluted at 50 with 200 parts of naphtha which is poured in slowly.

Under these conditions a varnish is obtained which, after filtration, dries in a few seconds at 450, in 3 minutes at 300, 3045 minutes at 200, 15-20 hours at 110.

The films obtained with this varnish, dried at 300, have a dielectric strength of 1520 volts to the one hundredth of a millimetre.

Example III 100 parts of the mass obtained under the conditions of Example No. I are diluted at by pouring on 200 parts of a mixture of benzene (63) toluene (63) xylene (63) coal tar oil (10). A varnish is obtained which dries under conditions similar to those of the previous varnishes.

Industrial benzols may of course be used instead of the above mentioned mixture.

Ewample I V 100 parts of the mass obtained under th I conditions of Example No. I are diluted at mentioned for the varnishes of Examples II I tore use.

6070' with 200 grammes of slowly added white petroleum. The varnish is filtered be- Under these conditions varnishes drying under conditions similar to those and III are obtained.

Examples'II, III and IV are not restricted with regardto the nature and proportions of solvent, and the nature of the resinous compound used. v a

. All-temperatures occurring in the specification are to be read as degrees 'centigrade.

I claim:

ing in an enclosed space under pressure a siccative oil and a synthetic resin having unesterified hydroxyl groups and formed by heating a polyhydric alcohol with amixture of a polybasic acidic compound and at least one natural resin, the heating of said oil and resin being carried out at a temperature sufiiciently high to roduce a soluble reaction product in which t e oil is chemically combined with said resin. I

2. As a new product, a resinous condensation product obtained by acting on glycerine with a mixture of phthalic anhydride and a natural resin in quantity sufficient to replace only a part of the free hydroxyl groups in the glycerine by the phthalic anhydride and a part by the resinic acid of the resin and leave some free hydroxyl groups remaining until a resinous mass is formed and heating this resinous mass under superatmospheric pressure with a siccative oil until a homogeneous'massis obtained in which the oil is chemically combined and which is soluble in I benzene and petrol derivatives.

3. Method of producing a, resinous condensation product which method consists in heating an aliphatic pplyhydric alcohol with amixture of a' poly asic acidic compound and at least one natural resin to obtain a resinous mass and heating the same with a siccative oil at about 210 C. for 16 hours under superatmospheric pressure and cooling at 50'60 C. until a homogeneous mass is obtained, and having the oil so combined that it cannot be separated, as in the case of a simple solution.

4. Method as defined in claim 3, wherein the aliphatic polyhydric alcohol employed is glycerine.

5. Method as defined in claim 3, wherein. the polybasic acidic compound employed is phthalic anhydride. y

6. A new resinous condensation product obtained 'by' heating in an enclosed space under pressure a siccative oil and a synthetic resin havin unesterified hydroxyl grou s and containlng a polyhydric alcohol radic e, a polybasic acid radicle, and a natural resin radicle, the heating to be carried out at a temperature sufliciently high to produce a soluble reaction product in which the oil is chemically combined with said reagent.

In testimony whereof I have hereunto affixed my signature.

ANDRE HENRI VICTORDURR.

"lo I l. The method of preparing a resinous condensation product which consists in heat- 

